CN109158058A - Recessed soil-chitosan plural gel and preparation method thereof - Google Patents
Recessed soil-chitosan plural gel and preparation method thereof Download PDFInfo
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- CN109158058A CN109158058A CN201811054046.6A CN201811054046A CN109158058A CN 109158058 A CN109158058 A CN 109158058A CN 201811054046 A CN201811054046 A CN 201811054046A CN 109158058 A CN109158058 A CN 109158058A
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000001879 gelation Methods 0.000 title description 6
- 239000000499 gel Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910021538 borax Inorganic materials 0.000 claims abstract description 21
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 21
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 19
- 239000000017 hydrogel Substances 0.000 claims abstract description 17
- 239000004964 aerogel Substances 0.000 claims abstract description 14
- 239000004927 clay Substances 0.000 claims abstract description 8
- 239000002689 soil Substances 0.000 claims description 57
- 239000000243 solution Substances 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 11
- 239000011268 mixed slurry Substances 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000003431 cross linking reagent Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000001815 facial effect Effects 0.000 abstract description 2
- 229960000892 attapulgite Drugs 0.000 abstract 3
- 229910052625 palygorskite Inorganic materials 0.000 abstract 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 239000008204 material by function Substances 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 235000000346 sugar Nutrition 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 1
- 206010052428 Wound Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000016127 added sugars Nutrition 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明涉及黏土深加工领域，公开了一种凹土‑壳聚糖复合凝胶及其制备方法，该复合凝胶由以下质量比的组分组成：凹土：壳聚糖：戊二醛：硼砂=100：12~35：1.2~5.25：3~5。本发明以凹土为主材、以壳聚糖为辅材，采用戊二醛与硼砂作为双交联剂，通过溶胶‑凝胶法制备凹土基复合水凝胶。本发明中的复合水凝胶具备优良的三维孔隙结构和力学性能，具有良好的吸附、缓释性能和固载能力，可用作面膜、药用敷料或组织工程支架等医药用功能材料，也可进一步冻干处理成用途更为广泛的气凝胶。该制备工艺所制得的气凝胶力学性能优异，弹性模量可在15~193Mpa范围内调控。本发明工艺简单，制备周期短，满足大规模化生产要求。
The invention relates to the field of deep processing of clay, and discloses an attapulgite-chitosan composite gel and a preparation method thereof. The composite gel is composed of components in the following mass ratios: attapulgite: chitosan: glutaraldehyde: borax =100: 12~35: 1.2~5.25: 3~5. In the invention, attapulgite is used as the main material, chitosan is used as the auxiliary material, glutaraldehyde and borax are used as double cross-linking agents, and the attapulgite-based composite hydrogel is prepared by a sol-gel method. The composite hydrogel in the present invention has excellent three-dimensional pore structure and mechanical properties, and has good adsorption, slow-release properties and immobilization capacity, and can be used as medical functional materials such as facial masks, medicinal dressings or tissue engineering scaffolds, etc. It can be further lyophilized into aerogels that are more versatile. The aerogel obtained by this preparation process has excellent mechanical properties, and the elastic modulus can be adjusted in the range of 15-193 Mpa. The invention has the advantages of simple process and short preparation period, and meets the requirements of large-scale production.
Description
Technical field
The present invention relates to clay field of deep, in particular to recessed native plural gel of a kind of chitosan-and preparation method thereof.
Background technique
Chitosan-based gel rubber material has excellent biocompatibility, biological degradability, nontoxicity, biocidal property and biology living
Property, it is bright in the numerous areas such as medicine, food, chemical industry, cosmetics, water process, biochemistry and biomedical engineering application prospect.It is poly-
Sugar has been put into national food additive and has used standard GB-2760.In recent years, the study found that under fluid environment, chitosan band is just
Charge, human body mucous membrane have negative electrical charge.Chitosan-based tissue engineering bracket material or wound dressing can have good with human body mucous membrane
Good biocompatibility, to promote regeneration and wound healing.Nevertheless, chitosan physical gel mechanical property pole
Difference causes it to be restricted in the application in many fields.Document has been reported that compound using nano-bentonite or carbon nano-fiber etc.
Promote the report of mechanical property, but reported plural gel be based on chitosan, the addition range of inorganic material≤
50wt%.Also aeroge can be prepared by freeze-drying in clay and high molecular polymer plural gel.Prepared at present
The aerogel-like density arrived is in 0.05-0.1g/cm3Between, reported best elasticity modulus is 12.24Mpa.
Summary of the invention
Goal of the invention: aiming at the problems existing in the prior art, the present invention provide a kind of recessed native plural gel of chitosan-and
Preparation method has excellent three dimensional pore structures and mechanical property by the plural gel that the preparation method obtains, has
It is good absorption and sustained release performance and immobilized ability, can be used as facial mask or medical dressing, can also further frozen dried at purposes
More extensive aeroge.
Technical solution: the present invention provides a kind of recessed native plural gels of chitosan-, are grouped as by the group of following mass ratio:
Recessed soil: chitosan: glutaraldehyde: borax=100:12 ~ 35:1.2 ~ 5.25:3 ~ 5.
The present invention also provides a kind of preparation methods of the recessed native plural gel of chitosan-, comprising the following steps: S1: prepares
The recessed soil paste material of 2wt% ~ 5wt%；S2: after the pH value of recessed soil paste material is adjusted to 4, appropriate 4wt% chitosan solution is added thereto simultaneously
It stirs evenly, suitable 2wt% glutaraldehyde solution stirring 30min is then added, continuously adds 0.4mol/L borax soln and stirs
Mixed slurry；S3: after gel 12h in mixed slurry injection highly basic weak solution, it is placed in aging 12h in deionized water at room temperature and obtains
The recessed native composite hydrogel of chitosan-.
It further, further include S4 after S3: by the recessed native composite hydrogel of the chitosan-at -80 ° ~ -196 DEG C
Freezing 5min must congeal glue, then will congeal glue progress frozen dried and obtain the recessed native composite aerogel of chitosan-.Obtained by frozen dried
Low (the 0.035g/cm of aeroge density3~0.055g/cm3), mechanical property is prominent, and (elasticity modulus can be adjusted between 15 ~ 193Mpa
Section).
Preferably, in S2, in recessed soil paste material it is recessed soil with chitosan solution in chitosan mass ratio be 1:0.12 ~
0.35。
Preferably, in S2, the quality of the glutaraldehyde in glutaraldehyde solution is the chitosan mass in chitosan solution
10%~15%。
Preferably, in S2, the additional amount of borax is the 3% ~ 5% of recessed soil paste material concave soil property amount.
Preferably, the highly basic weak solution is sodium hydroxide or lithium hydroxide.
Preferably, the concentration of the highly basic weak solution is the wt% of 0.3wt% ~ 0.45.
Further, in S1, the preparation method of recessed soil paste material is as follows: recessed soil being crushed to 200 mesh, with 2wt% acetic acid acid
Change 6h, after centrifugal sedimentation discards the non-clay impurity of lower layer, slurry is reconfigured as to the recessed soil paste material of 2wt% ~ 5wt%.
The utility model has the advantages that the present invention using it is recessed soil for main material, using chitosan as auxiliary material, chitosan-is prepared using sol-gal process
Recessed soil composite hydrogel has the advantage that compared with prior art
(1) the innovation of the invention consists in that it is recessed soil be main material, accounting 70%-90%, in the prior art based on chitosan,
Chitosan-recessed native plural gel of the recessed soil in 5-10% or so is compared, and preparation cost reduces significantly, and due to chitosan gel rubber
Mechanical strength it is very low, the introducing of a large amount of recessed soil can assign the faster gelation rate of plural gel and good in the present invention
Mechanical property；While keeping chitosan gel rubber good biocompatibility, the introducing of the recessed soil of fibrous type can Effective Regulation it is solidifying
Glue pore structure；Raw material of the present invention is natural green material, safety and environmental protection and simple process；
(2) since recessed soil paste material itself is alkalescent, chitosan can only be dissolved in acid, if it cannot be guaranteed that mixed liquor is acid enough,
Then recessed soil is difficult to disperse sufficiently with chitosan；And the present invention with it is recessed soil for main material, so being first adjusted with acid recessed soil paste in the present invention
The pH of material is mixed to 4 or so, then with 4wt% chitosan solution, advantageously reduces system viscosity, promotes recessed soil compound with chitosan
Thoroughly.
(3) mixed slurry is injected gel in highly basic weak solution by the present invention, and the processing of highly basic weak solution is mild gelation, forms three
It is more uniform intact to tie up network.The present invention is aeroge via mild gelation and frozen dried, gained gel, and density drops significantly
Low, porosity is abundant.
(4) organic crosslinking agent and inorganic crosslinking agent are used cooperatively in the present invention, first put organic crosslinking agent glutaraldehyde, it is basic to be crosslinked
Add inorganic crosslinking agent borax again afterwards, two kinds of crosslinking agents synergistic effects while ensure that the extremely-low density of gel, are greatly promoted
The mechanical mechanics property of plural gel.
It (5) is in the prior art usually that crosslinking agent is added after gel, crosslinking agent is by diffusing into gelinite at this time
Inside, and then be crosslinked, so the degree of cross linking is successively decreased with the diffusion concentration of crosslinker concentration, crosslinking is uneven, it is not easy to control；
And the invention patent is the crosslinking agent added before gelation, crosslinking and gel carry out simultaneously, are crosslinked to be homogeneous, to the three of gelinite
It is more accurate to tie up network regulation.
Detailed description of the invention
Fig. 1 is the recessed native composite hydrogel hydraulic pressure test outside drawing of 1 chitosan of example-；
Fig. 2 is that the recessed soil of 2 glutaraldehyde cross-linking of example-chitosan composite aerogel and glutaraldehyde-recessed soil-chitosan of borax double cross connection are multiple
Close the microcosmic SEM figure of aeroge；
Fig. 3 is the recessed native composite aerogel outside drawing of 3 chitosan of example-.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawing.
Embodiment 1:
Present embodiment improves a kind of recessed native plural gel of chitosan-, and be grouped as by the group of following mass ratio: recessed soil: shell is poly-
Sugar: glutaraldehyde: borax=100:12:1.44:3.
Recessed soil is crushed to 200 mesh, with 2wt% acidifying with acetic acid 6h, centrifugal sedimentation discards the non-clay impurity of lower layer, then will
Slurry is reconfigured as the recessed soil paste material of 2wt%, and adjusts the pH to 4 or so of recessed soil paste material, and then appropriate 4wt% chitosan is added
Solution (wherein, the mass ratio of the recessed soil in recessed soil paste material and the chitosan in chitosan solution is 1:0.12), and stir evenly,
Continuously adding suitable 5wt% glutaraldehyde solution stirring 30min, (wherein, the glutaraldehyde dosage in glutaraldehyde solution is chitosan
The 12% of chitosan mass in solution), continuously adding the stirring of 0.4mol/L borax soln, (wherein, borax dosage is recessed soil paste material
The 3% of concave soil property amount), obtain mixed slurry.Then mixed slurry is injected into gel 12h in 0.4wt% lithium hydroxide solution, then
It is placed in aging 12h in deionized water at room temperature, obtains the recessed native composite hydrogel of chitosan-.Composite hydrogel is cold at -196 DEG C
Glue must be congealed by freezing 5min, will finally be congealed glue progress frozen dried and be obtained the recessed native composite aerogel of chitosan-.Preparation gained is compound
The density of aeroge is 0.037g/cm3, elasticity modulus 20Mpa.
Fig. 1 is the hydraulic pressure test outside drawing of the recessed native composite hydrogel of chitosan-in present embodiment, as can be seen from the figure
After water slug, composite hydrogel still keeps completely, illustrating that hydrogel has excellent mechanical performance.
Embodiment 2:
Present embodiment improves a kind of recessed native plural gel of chitosan-, and be grouped as by the group of following mass ratio: recessed soil: shell is poly-
Sugar: glutaraldehyde: borax=100:25:2.5:4.
Recessed soil is crushed to 200 mesh, with 2wt% acidifying with acetic acid 6h, centrifugal sedimentation discards the non-clay impurity of lower layer, then will
Slurry is reconfigured as the recessed soil paste material of 3.5wt%, and adjusts the pH to 4 or so of recessed soil paste material, and then it is poly- that appropriate 4wt% shell is added
Sugar juice (wherein, the mass ratio of the recessed soil in recessed soil paste material and the chitosan in chitosan solution is 1:0.25) simultaneously stirs equal
Even, continuously adding suitable 5wt% glutaraldehyde solution stirring 30min, (wherein, the glutaraldehyde dosage in glutaraldehyde solution is poly- for shell
The 10% of chitosan mass in sugar juice), continuously adding the stirring of 0.4mol/L borax soln, (wherein, borax dosage is recessed soil paste
Expect the 4% of concave soil property amount), obtain mixed slurry.Then mixed slurry is injected into gel 12h in 0.3wt% sodium hydroxide, then room
It is placed in aging 12h in deionized water under temperature, obtains the recessed native composite hydrogel of chitosan-.Composite hydrogel is freezed at -196 DEG C
5min must congeal glue, will finally congeal glue progress frozen dried and obtain the recessed native composite aerogel of chitosan-.The compound gas of preparation gained
The density of gel is 0.042g/cm3, elasticity modulus 40Mpa.
Fig. 2 is that the recessed soil of glutaraldehyde cross-linking-chitosan composite aerogel and glutaraldehyde-borax double cross connection are recessed in present embodiment
Soil-chitosan composite aerogel microcosmic SEM figure.It can be seen from the figure that glutaraldehyde-borax double cross connection composite aerogel and list
One glutaraldehyde cross-linking composite aerogel is compared, and interparticle distance is more fine and close.Illustrate that this method can further promote compound airsetting
The mechanical property of glue.
Embodiment 3:
Present embodiment improves a kind of recessed native plural gel of chitosan-, and be grouped as by the group of following mass ratio: recessed soil: shell is poly-
Sugar: glutaraldehyde: borax=100:30:4.5:5.
Recessed soil is crushed to 200 mesh, with 2wt% acidifying with acetic acid 6h, centrifugal sedimentation discards the non-clay impurity of lower layer, then will
Slurry is reconfigured as the recessed soil paste material of 4wt%, and adjusts the pH to 4 or so of recessed soil paste material, and then appropriate 4wt% chitosan is added
Solution (wherein, the mass ratio of the recessed soil in recessed soil paste material and the chitosan in chitosan solution is 1:0.3), and stir evenly,
Continuously adding suitable 5wt% glutaraldehyde solution stirring 30min, (wherein, the glutaraldehyde dosage in glutaraldehyde solution is chitosan
The 15% of chitosan mass in solution), continuously adding the stirring of 0.4mol/L borax soln, (wherein, borax dosage is recessed soil paste material
The 5% of concave soil property amount), obtain mixed slurry.Then mixed slurry is injected into gel 12h in 0.45wt% sodium hydroxide, then room
It is placed in aging 12h in deionized water under temperature, obtains the recessed native composite hydrogel of chitosan-.Composite hydrogel is freezed at -196 DEG C
5min must congeal glue, will finally congeal glue progress frozen dried and obtain the recessed native composite aerogel of chitosan-.The compound gas of preparation gained
The density of gel is 0.048g/cm3, elasticity modulus 170Mpa.
Fig. 3 is the recessed native composite aerogel outside drawing of chitosan-in present embodiment, it can be seen from the figure that passing through the party
Method can prepare the complete block aeroge of Ultra light-weight extremely-low density.
The technical concepts and features of above embodiment only to illustrate the invention, its object is to allow be familiar with technique
People cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
The equivalent transformation or modification that Spirit Essence is done, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of recessed native plural gel of chitosan-, which is characterized in that be grouped as by the group of following mass ratio:
Recessed soil: chitosan: glutaraldehyde: borax=100:12 ~ 35:1.2 ~ 5.25:3 ~ 5.
2. a kind of preparation method of the recessed native plural gel of chitosan-as described in claim 1, which is characterized in that including following
Step:
S1: the recessed soil paste material of 2wt% ~ 5wt% is prepared；
S2: after the pH value of the recessed soil paste material is adjusted to 4, appropriate 4wt% chitosan solution being added thereto and stirs evenly,
Then suitable 2wt% glutaraldehyde solution stirring 30min is added, continuously adds 0.4mol/L borax soln and stirs to obtain mixed slurry；
S3: after gel 12h in mixed slurry injection highly basic weak solution, it is placed in aging 12h in deionized water at room temperature and obtains
The recessed native composite hydrogel of chitosan-.
3. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that after S3, also
Including S4: the recessed native composite hydrogel of the chitosan-is freezed 5min under -80 ° ~ -196 ° must congeal glue, then will congeal
Glue carries out frozen dried and obtains the recessed native composite aerogel of chitosan-.
4. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that described in S2
The mass ratio of recessed soil in recessed soil paste material and the chitosan in the chitosan solution is 1:0.12 ~ 0.35.
5. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that described in S2
The quality of glutaraldehyde in glutaraldehyde solution is 10% ~ 15% of the chitosan mass in the chitosan solution.
6. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that described in S2
The additional amount of borax is the 3% ~ 5% of the recessed soil paste material concave soil property amount.
7. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that described in S3
Highly basic weak solution is dilute solution of sodium hydroxide or lithium hydroxide weak solution.
8. the preparation method of the recessed native plural gel of chitosan-according to claim 2, which is characterized in that described in S3
The concentration of highly basic weak solution is the wt% of 0.3wt% ~ 0.45.
9. the preparation method of the recessed native plural gel of the chitosan-according to any one of claim 2 to 8, which is characterized in that
In S1, the preparation method of the recessed soil paste material is as follows:
Recessed soil is crushed to 200 mesh, with 2wt% acidifying with acetic acid 6h, after centrifugal sedimentation discards the non-clay impurity of lower layer, by slurry weight
Newly it is configured to the recessed soil paste material of 2wt% ~ 5wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942904A (en) * | 2019-02-28 | 2019-06-28 | 淮阴工学院 | A kind of attapulgite composite chitosan gel and preparation method thereof |
| CN110813247A (en) * | 2019-10-25 | 2020-02-21 | 淮阴工学院 | Preparation method and application of attapulgite-based chitosan aerogel adsorbent |
| CN113210022A (en) * | 2021-05-12 | 2021-08-06 | 北京工业大学 | Preparation method of Cu-attapulgite-chitosan chelate microsphere catalyst applied to catalytic wet oxidation |
| CN113680288A (en) * | 2020-05-18 | 2021-11-23 | 淮阴工学院 | Preparation method of hydrophobic attapulgite composite aerogel |
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| CN113680288A (en) * | 2020-05-18 | 2021-11-23 | 淮阴工学院 | Preparation method of hydrophobic attapulgite composite aerogel |
| CN113210022A (en) * | 2021-05-12 | 2021-08-06 | 北京工业大学 | Preparation method of Cu-attapulgite-chitosan chelate microsphere catalyst applied to catalytic wet oxidation |
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